Process of regenerating catalytic material



y UNITED STATES PATENT (OFFICE.

CARLETON ELLIS, OF MONTCLAIR, NEW JERSEY.

PROCESS OF REGENERATING CATALYTIC MATERIAL.

No Drawing. Original application filed November 24, 1916, Serial No.

Specification of Letters Patent.

Patented Sept. 13, 1921. 133,252. Divided and this application filed ma1, 1917. Serial No. 165,763.

To all 1071 om it may concern Be it known that I, CARLETON citizen ofthe United States, residin Montclair, in the county of Essex and tate ofNew Jersey, have invented certain new and useful Improvements inProcesses of egenerat-ing Catalytic Material, of which the following isa specification.

The present invention relates to the regeneration of a catalyst used inhydrogenating, and particularly adapted for the hydrogenation of oilscontaining unsaturated components and other unsaturated organicmaterials, by the decomposition of salts of catalytic metals with formicor other lower fatty acids, while carried in oil or other orgamevehicle,solely by heat ng, or by heating with the simultaneous lntroductlon ofan inert or non-reducing gas, such as nitrogen and in some cases carbondioxid, and the like. Hydrogen or gases containmg hydrogen, such aswater gas, or gases containing carbon monoxi'd, such as watergas orproducer gas are to beavoided, these materials being reducing agents andnot inert gases. In my prior applications 656,100 filed October 23. 1910(now Patent 1,026,156), 686,988 filed March 29, 1912-(now Patent1.217.118). 808.461 filed December 23, 1913, 817.011 filed February 26,1914 (now Patent 1.251202), 50,492 filed September 13, 1915. 89,093filed April 5, 1916 and others, I have described the product-ion ofcatalysts by the treatment of certain reducible compounds of nickel andcertain other catalytic ELLIS, a at metals, e. 9 oleat-es of nickel andof other like metals, in a bath of oil, for example by treatment with areducing gas such as hydrogen. The present application is for matterconstituting a continuation or an mprovement in the processes of theforegolng applications and is a division of my c0pend-- ing application133,252, wherein the treatment of nickel and similar oleates isspecifically claimed.

Various gases and volatile bodies are liberated during the decompositionof some metallo-organic compounds, which tend to retard the reaction,particularly if allowed to remain confined within the material, andthese gases also appear to have some action on the catalyst itself.particularly if the said gases are allowed to accumulate in the mixtureundergoing reaotion, to a conslderable extent.

products of the metallo-organic compound under treatment, which actiontends to prevent deleterious modification of the texture of the catalystor coagulation thereof while the same is being produced.

As examples of the particular materials to be decomposed, I mentionnickel formate, copper formate, or the double acetates (eg.nickel-copper acetate) or double formates (e. 9-, nickel-copper formate)or mixture of two or more of the above-mentioned bodies.

I call attention to the fact that it is not necessary to restrict theamount of the metal compound to an amount capable of furnishmg thequantity of catalytic metal sufficient for the catalytic hydrogenationof the oil under treatment, but in some cases I preferably employ aconsiderable excess of the salt of the catalytic metal, in order toproduce a catalyzer concentrate, which may be added o a relatively largeamount of oil, prior to h drogenation of said oil. Thus for example, mayemploy a mixture of an oil carrying 12' to 25% of one of themetalloorganic compounds to be employed, such as those above referredto, or of a mixture of such compounds.

The temperature to -which the oil and metallo-organic body will beheated will depend upon the nature of the particularv metallo-organicmaterial, and to a certain extent upon the character of theoily vehicle.Upon the particular temperature used will depend to some extent, thecharacter. of the product. lVhen using nickel formate and cottonseedoil, a vacuum of 29-3O inches of mercury and a temperature of about 200C. for several hours may be used. Somewhat higher temperatures are,however, preferred in carrying out the process. \Vhen heating thismixture, I preferably bubble nitrogen gas (essentially free from oxygenand 60, although a small amount of C- 2 usually is not disadvantageous)slowly therethrough, the partial vacuum above referred to preferablybeing maintained,

specified, the action of catalyzer thereby formed is somewhat bet terthan the catalyzer produced at 200 C. The reduction of, for example,nickel formate, at a temperature below but near 200 C, when carried outunder reduced atmospheric pressure does not afford a very efiicientcatalyzer. The simple heating of the formats or analogous salt of afatty acid in an open vessel especially with a current of an inert gaspassing through the oil while heating to temperatures approximatelybetween 230 and 250 C., enables catalytic material of a highly effectivecharacter and satisfactory texture to be simply and cheaply preparedwithout resorting to expensive and elaborate apparatus or to use aseries of costly steps to produce catalytic material adapted for thehydrogenation 'of oils. Catalyzer may be prepared in accordance with myinvention, which has good filtering qualities.

In heating up a metallo-organic compound of the character described,including a mixture of several formates, or other salts of the lowerfatty acids, the temperature is raised to at least the decompositionpoint and preferably is held at least 10 or so above such decompositionpoint and the catalyzer prepared in this manner is suitably collected,or the reduction may be caused to take place in a suitable oily vehicleto produce the catalyzer concentrate which may be suitably diluted withthe oil to be hydrogenated to give approximately one half of one percent. or thereabout of the catalytic material. Hydrogen is thenintroduced while the oil is maintained at 160-190 C. until hydrogenatedto the desired extent.

By heating such nickel or other compound to at least the decompositionpoint or preferably 10 higher as stated, and in passing through th oilyvehicle a current of an inert gas the removal of deleterious gases andproducts of reaction of a volatile character is effected so that thesegases or volatile decomposition products are not allowed to act upon thecatalyzer which is forming or has been formed and thus the catalyticmaterial is preserved in a state of purity which is highly desirable,and extensive action on the oil is also prevented.

The oil employed may be a fatty or mineral oil, and obviously should besufficiently free of catalyzer poisons or of materials capable ofexerting any untoward action on the catalyst, which is especiallysensitive to injury while in a nascent state. All detrimental traces ofsulfur, chlorin, (sometimes free oxygen) and the like should accordinglybe first removed from the oil if present therein, preferably beforeadding the metallo-organic body thereto. 0

;For most purposes it is advisable to conduct the decomposition reactionin a body of oil of the same kind and quality (or a similar kind orquality) as the oil with which the catalytic material is to be employed.

It will be obvious that the oily material which forms the reactionvehicle will also form the sealing fluid or medium for the producedcatalyst. If this oil be one which is solid or semi-solid at normalatmospheric pressures, the product may be run into receptacles or moldsand allowed to harden, after the reaction is completed. The castingsthereby produced may be stored for subsequent use as catalyst material,may be shipped, etc., to plants where the same is to be used, and sincethe solidified oil forms a seal, the catalyst is protected thereby fromthe action of air and other deleterious influences. It is advisable,however, to suit ably seal up such packages, directly or shortly afterthe production thereof.

1 call attention to the fact that this invention is not restricted tosalts of the acids mentioned, or to salts of the metals stated. Salts ofvarious organic acids are suitable, (especially the salts of the lowerfatty acids) in addition to the for-mates specifically de scribed, andsalts of any acid, which when heated will decompose and liberate freemetal, may be employed. Formates and similar salts of metals other thancopper and nickel, notably the salts of the metals having atomic weightsbetween 56 and (34:, are suitable for use in my present invention.

The metals may be set free in a nonsettling condition of fineness, inwhich condition they are especially suited for use as catalysts inhydrogenation of oils and other organic bodies, and for other purposes.

A distinct advantage is found to result in the use of a partial vacuumand the absence of introduction of reducing gases, in that such gases,present while the catalyst is being produced (while in a nascent state)and particularly if under high pressures, appear to alter the physicalstructure of the metal to make it more dense and less catalyticallyactive, or otherwise of not the best possible character, as for example,becoming coagulated and ineffective after use for a short time. Theunfavorable properties in question appear, in at least some instances,to be produced by the continued presence, in the reaction mixture, ofthe non-metallic reaction products, such as water, carbon monoxid,hydrogen, formic acid and other acids, etc. By the use of vacuum, and bypassing a current of inert' gas through the reaction mass, theseproducts are rapidly carried away, and out of contact with the nascentmetal being formed or at least it reduces the amount of such productspresent with the said nascent metal,

formate may be coagulation. over As above Stated, the metal produced inthe preferred form of this process is in an extremely attenuated andfinel divided state, highly conducive to catalytic activity. It may berepeatedly used without danger of a considerable period. lVithoutlimiting myself to particular metals, I will state that the process ofthe present application is highly effective in the production of thecatalytic metals having an atomic weight between 56 and 64.

The metallo-organic salts employed herein may be prepared in variousways. Xickel prepared by dissolving nickel carbonate or hydrate informic acid. The freshly precipitated carbonate or hydrate is moreeffective in yielding a salt of the character desired Acid, basic andneutral compounds of formic acid may be produced, the referable onebeing the neutral 'formate. The salts preferably should be prepared "ina substantially pure condition, as by using chemicals free fromcatalyzer poisons, etc., or by effective washing of the product whenfeasible, so as to free it from any catalyzer poisons that may bepresent in prejudicial amount. the acetate and corresponding salts ofanalogous aliphatic or fatty acids may be prepared from basic nickelcarbonate or hydrate in afreshly precipitated state.

The temperature employed in the process, as above stated, may vary moreor less. While using hydrogen gas, or other reducing gas, as in therocesses in my other cases above referred to, temperatures below 200 C.,particularly temperatures from 160 or 180 to 200 C. may be used. Withoutusing hydrogen, the best temperature for the decomposition of nickelformate appears to lie in the neighborhood of 230 to 240 C. At thesetemperatures very finely divided nickel, in a substantially colloidalcondition, and possessing strong magnetic properties, is obtained.

It appears probable that with some of the .metallo-organic compoundsmentioned, while no reducing gas is added or brought into the solutionor mixture from outside, the decomposition of a dportion of the organicacid,

within the ho ring substantia l decomposition o the metallo-organiccompound, or else while the said organic acid set free is in the nascentcondition, some reducing gases may be formed. In some of the appendedclaims,

of oil, for example occur In a similar manner simultaneously with the.

I have used the expression in the absence of added reducing gases, whichexpression is not intended to imply that such reducing gases asareformed' in the process itself may not have the same reducing actionupon the metallo organic compound. It even appears asbein possible thata part of the reduction of the nickel compounds is effected in a zone ofgases of reducing character, produced by self-decom position of themetallo-organic. compounds.

he regeneration of the catalytic material is preferably carried out bydissolving the spent catalyzer, preferably previously extracted withbenzol to remove fats, etc., in nitric acid and precipitating withsodium carbonate or caustic soda solution to yield a moist carbonate orhydrate and then reacting upon this moist precipitate with formic acidor acetic acid and the like. It is not necessary in all cases to actupon the wet pre- 'cipltatei drate may be dried but in such case it isdesirable to carry out the drying so as to not contract the nickelhydrate particles as to interfere with their ready solution in the acidsolvents.

The salt thereby produced will thereafter be decomposed in the .mannerabove described.-

What I claim is:

1. The process of regenerating catalytic nickel material which comprisesfreeing the catalytic material to a large extent from fatty or oilymaterial, dissolving the residue in nitric acid, precipitating thenickel from the nickel solution as a basic compound, in reacting uponthe basic material in the freshly precipitated condition with formicacid, whereby a nickel formate is obtained and in subsequentlydecomposing such salt by heating to a. temperature at or above thedecomposition point.

2. The process of regenerating catalytic nickel material used in thehydrogenation of oils'which comprises freeing the catalytic material toa large extent from fatty or'oily material, dissolving the residue in anacid, precipitating the nickel from the nickel solution as a basiccompound, in reacting upon the basic material in'thefreshly precipitatedcondition with a fatty acid to produce a salt of the fatty acid and insubsequently decomposing such salt by heating to a temperature at orabove the, decomposition point, in a bath of oily material.

testimony whereof I aflix m si nature.

' .oAR LEToN EfiLIs.

Freshly precipitated nickel by"

